Process for the separation of hydrocarbons



Nov. 19, 1940. D. F. BABCOCK 2,222,275

PROCESS FOR THE SEPARATION OF HYDROCARBONS Filed Oct. 14, 1937 Co mpressor fiafmos.

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Com resser c001 er Cqolir Gas 24 Gasflli uid Separa or i i" aaafmos PUMP (in: (f L quid .iepara for Propylene Prapyiepz rafmq Means Da/e ff Babcock INVENTOR.

BY a -W ATTORNEY Patented Nov. 19, 1940 I t UNITED STATES PATENT OFFICE PROCESS FOR THE SEPARATION OF HYDROCARBON S Dale F. Babcock, Wilmington, Del., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware Application October 14, 1937, Serial No. 168,890 6 Claims. (CI. 196-7) This invention relates to a process for the ably about four and about eleven'atmospheres purification of normally gaseous mixtures, and respectively. more particularly to the purification oi the (2) The liquids condensed on interstage coolgaseous products produced by the cracking of ing are separated from the gas and combined petroleum, and still more particularly to the with the eflluent from the next higher compresseparation of a gaseous hydrocarbon mixture into sion stage. a gaseous fraction containing predominantly ('3) The gas and liquid mixture obtained at 33 propylene and more volatile components and into atmospheres is cooled to such a t ure at a liquid fraction containing predominantly an appreciable quantity of C3 hydrocarbon is 0 propylene and less volatile components. condensed. The pyrolysis of petroleum materials, as prac- (4) This liquid is separated from the vapor ticed in commercial vapor phase cracking operand rectified 80 that the resulting q d s S- ations, produces both liquid and gaseous pr0d sentially ethane free. ucts. These cracked gases are usually saturated The accompanying drawing represents dia- 5 with materials boiling in the gasoline range grammatically a complete apparatus for the sepwhich must be recovered prior to use of the gas aration of the components of the fluid mixture in other processes or for fuel. referred to above. Reference will be made to this In the gasoline refining industry this recoveryv drawing in order to properly describe the invenof gasoline is often efiected by compressing the tion. It is to be undertsood that the details of l cracking gas to amoderate pressure, cooling, and th s apparatus, which are well known to those 30 thereby liquefying a portion of its gasoline con- Skilled in the art, have been omitted for the sake tent. The uhcondensed gases, still under presof clarity and the modifications in the details sure, are then forced up through a scrubbing of'construction d in arrangement of parts y tower, countercurrent to a light oil which scrubs be made Without departing f om th Sp r t of the I the remaining gasoline from the fixed gases. e tio The low-boiling gasoline is then distilled from The hydrocarbon vapor to be Processed the "fat oil, which is then recycled to the scrube s the syst m t r u h c uit 2 a app ox bing operation. The distillate is joined with the mately atmospheric pr ssure. The gas is comliquid fraction separated after compression, and p ess d n c p o 4 o pp o a e y 4 atthe mixture is introduced into a stabilizing colmospheres absolute. and it is Passed through 80' umnwhere the low-boiling components which a conduit 6 and water cooler 8 into separator l0 too volatile to be used in gasoline are distill d where the condensed liquid is separated from the on. I have found it much more expedient to regas. The gas free of con ensed liquid is p sed cover and to stabilize the gasoline content of the through conduit M to compressor I8 where its cracked gas in a different manner. pressure is increased to approximately 11 atmos- This invention has as its object the separation ph e The liq i fr m separator I0 is forced of a normally gaseous hydrocarbon mixture into y pump [2 throug conduit 5 into conduit a gas fraction containing predominantly prowhere it mixes with the compressed vapors from pylene and more volatile components and'into a compressor This combined gas and q id liquid fraction containing predo ninantly promixture is passed through water 000161 22 and pylene and less volatile components. A further the Condensed iq Separated from e gas in object is to obtain this separation. with a miniepa The gas is p ssed through conduit mum expenditure of power. A still furthe b.. into compressor 32 where its pressure is-raised ject is to reduce the water content of the gaseous t approximately 33 s s. The liquid in fractions significantly below that existing in the separator." is forced by p 6 through conoriginal i t th object is t provide duit 28 into conduit 34 where it combines with an apparatus for th accomplishment of t the eflluent from compressor 32. The combined above ends. Other objects will appear hereinliquid nd gas i oled in Water cooler 35 to after. approximately room temperature and further These objects are accomplished by processing a cooled to nearly 0 C. in cooler 38 which is sup- 5 hydrocarbon gas according to one or more of the plied with a suitable refrigerant. The cooled following steps in combination, fluid from cooler 38 is conductedyia conduit 40 (1) The gas is compressed to about 33 atmosto the gas and liquid separator 42. The gas pheres using two or more stages. When three is separated from the liquid in separator 42, the es are used the intermediate stages are suitgas passing through conduits 44 and and out essentially all of the of the system. The liquid from separator 42 passed through conduit 46 into rectifier 48. The calandria 50 at the base of this rectifier is heated using high pressure steam or other media so that ethane and more volatile components are expelled from the liquid. Condenser 56. located'at the top of rectifier 48, is

cooled to nearly C. using a suitable refrigerant. The non-condensab-le gas leaving the top of the rectifier through conduit 58 is combined with the gas from separator 42 which passes through conduit 44 and passed out of the system through conduit 60. The liquid is conducted via conduit 52 from the base of the rectifier and is expanded through valve 64 and may be either further rectified in suitable equipment or stored in tanks.

In order to avoid polymerization or gum formation in the calandria 50, the boiling temperature existing within said calandria may be reduced from 10 to 20 C. by the addition of propylene thereto. This propylene may be obtained from the liquid conducted via conduit 52 by drawing ofi some or all through conduit 53. This can be accomplished by the adjustment of valves 54 and 64.

The liquid so conducted is introduced into propylene separating means 62 and the propylene so separated recycled through conduit 66 to calandria- 50. The resulting liquid from which the propylene has been separated is removed via conduit ,68 for further treatment.

The propylene may be separated by any conventional method such as expanding the liquid containing same into a. flash chamber and recompressing the off-gas to condense same prior to returning to the calandria, or by fractionally distilling so as to obtain a liquid propylene fraction.

Example A gas of the following composition prepared by the vapor phase cracking of petroleum was used as the crude material for the operation of this invention.

The components of this gaseous mixture less volatile than ethane were essentially oleflnic in character. Cyclic compounds such as benzene and toluene were also known to be present. The crude gas of the above composition was compressed to 4 atmospheres and cooled to 35 C. Liquid amounting to some 5 mol per cent of the total gas and having the following composition was condensed by this operation.

Moi Composition: per cent Propylene and lighter hydrocarbons-.." 5 C4 hydrocarbons 5 C5 hydrocarbons Co hydrocarbons and heavier hydrocarbons Total The gas at 4 atmospheres was compressed to 11 atmospheres, combined with the liquid condensed in the first stage after-cooler and'the resulting mixture cooled to 35 C. This operation condensed 15 mol per cent on the crude gas. The liquid has the following composition:

Moi Composition: per cent Ethylene and lighter hydrocarbons 7 Ca hydrocarbons 16 10 C4 hydrocarbons 14 Ce hydrocarbons 16 Cs and heavier hydrocarbons 47 Total 100 15 The gas at 11 atmospheres was compressed to 33 atmospheres, combined with the liquid condensed at 11 atmospheres and the mixture cooled to 5' C., at which temperature some 48 mol per cent 20 of the original gas had been liquefied. This liquid had the following composition:

- M01 Composition: per cent Methane 6.2 Ethy e 19.1 Ethane 14.3 C3 hydrocarbons 27.4 C4 hydrocarbons 9.8 C5 hydrocarbons 6.7 Ca and heavier hydrocarbons 16.5

Total 100.0 This liquid was rectified at 33 atmospheres and a tails product produced at +130 C. which 85 amounted to some 26 mol per cent of the crude gas and had the following composition: M

01 Composition: per cent Ethane 0.2 Ca hydrocarbons 40.0 CI. hydrocarbons 17.6 C5 hydrocarbons 12.2 C6 and heavier hydrocarbons 30.0

Tota 100.0 Reflux in the rectifier was produced by a condenser which lowered the temperature of the gas leaving the top to +5 C. This vent gas had the following composition:

M01 Composition: per cent Methan 13.9 Ethyle 42.7 Ethane 31.9 C3 hydrocarbons 11.5 C4 hydrocarbons 0.0

Total 100.0 The vent gas was combined with the high pressure gas leaving the separator, producing a fraction which amounted to some 74 mol per cent of the crude gas. This gas fraction had the following composition:

M01 Composition: per cent Hydrogen 15.0 Methane 23.9 Ethylen 30.1 Ethane 18.4 C: 11.1 1.1 Cu 0.4

Total 100.0

' reduced to approximately one tenth of one per cent and was further reduced to nearly three one-hundredths of .one per cent by cooling the gas to +5 C. The water that was condensed with the various gasoline fractions was allowed to carry on through the system along with'the liquid products and was removed alongwith the The above described compression system employs three stages in order to raise thevpressure of thegastothatdeslred. Alessoragreater number of compression steps may be used without departing from the spirit of this invention. The final pressure employed in the above example was 33 atmospheres. The pressure used in any given case will in a measure depend upon the disposition to be made of the cold gases leaving the final separator and rectifier. For gas mixtures of composition similar to those given above the final pressure stage is from about 30 to 35 atmospheres absolute but somewhat higher or lower presures are operable and are of advantage in some cases.

In order to obtain maximum propylene condensation, it is desirable to use a low temperature in the refrigerated cooler, that is, a temperaturebelow 25 C. The temperature of 5 C. used in the example was chosen since it is sufficiently above C. that ice formation is not encountered, and it is sumciently cold to condense adequate quantities of propylene. If. for example, it is not desired to condense propylene but butylene is desired as the most volatile component in the liquid produced at the base of the rectifier, higher temperatures than C. may be employed.

In order that a larger proportion of the propylene may be withdrawn with the liquid fromthe base of the rectifier, butylene or a less volatile hydrocarbon may be pumped into the gas stream prior to cooling in the low temperature cooler. This recycled hydrocarbon may be conveniently obtained by distilling the tails liquid from the rectifier, removing the propylene, and recycling the resulting material.

With certain gas compositions, difiiculty is experienced due to polymerization or gum formation in the calandria of the rectifier which in the above example is heated to approximately +130 C. To avoid such polymerization the boiling temperature existing within this calandria may be reduced by some to C. without contamination of the resulting liquid with ethane and lighter boiling material if additional propylene is recycled into the The process and apparatus disclosed herein may be used for the separation of other fluid mixtures into a gas component and a. liquid component. This invention, however, is most usefully employed as a separate processing step prior to the hydrocarbon liquids from the base of the recti-' fier system is reduced by some 26%, over a process in which the gasoline fraction is separated free of lower boiling components. Since the low temperatures required in the liquefaction system are costly to produce, any reduction in the volume of material handled produces attractive savings.

The liquid produced at the base of the rectifier contains as its most volatile component, proylene. For this reason, the removal of this material as a pure fraction in the subsequent distillation step can be accomplished in a single step.

The method of propylene and gasoline recovery described herein also gives preliminary drying of the gas; e. g., the water content of the gas is reduced to its equilibrium vapor pressure at approximately 0 C. Under these conditions the gas may be passed directly into a heat exchanger and further cooled to, say, approximately -50 C., and the volume of water condensed to a solid will be relatively small, thus allowing a long time interval before thawing is required.

- As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to the specific embodiments thereof except as defined inthe appended claims.

I claim:

1. A process for the separation of the gaseous hydrocarbon mixture produced by the cracking of petroleum hydrocarbons into a gaseous fraction containing predominantly propylene and more volatile components and a liquid fraction containing predominantly propylene and less volatile components which comprises compressing said cracked gaseous petroleums to a pressure ofabout 3 atmospheres, cooling said gas to room temperature and separating any condensed liquid from the uncondensed gases, compressing the uncondensed gases thus separated to a pressure of about 11 atmospheres, combining with the compressed gas the liquid separated in the preceding gas and liquid separation step, cooling the resulting mixture to room temperature and separating the liquid fraction from the gaseous fraction, further compressing the separated gaseous fraction to about 33 atmospheres, combining with said gaseous fraction the liquid from the second gas and liquid separation step, cooling the resulting fluid mixture to about +5 C. and separating the liquid fraction from the gaseous fraction, rectifying the liquid fraction at a pressure of about 33 atmospheres by countercurrent flow of reflux liquors, by boiling the liquid at the base of the rectifying column at a temperature of about 130 0., and condensing the refiux liquors at the top of said column at a temperature of about +5 C.

2. The process which comprises compressing in at least two stages to a pressure of about 33 atmospheres in the last stage a gaseous mixture produced by the cracking of a petroleum hydrocarbon and comprising ethane and propylene, cooling and separating condensed liquid between the compression stages, combining the liquid thus separated on interstage cooling with the efiluent from the next higher compression stage, cooling the mixed liquid and eflluent from the last compression stage to a temperature sufiicient to condense an appreciable quantity of the three carbon atom hydrocarbon, separating this condensed liquid from the gas and rectifying the liquid out of contact with the previously separated gas under conditions which will result in a liquid fraction substantially free of ethane, separating propyleneirom the final liquid fraction and recycling same to the fractionating system.

3. The process which comprises compressing in at least two stages a gaseous hydrocarbon mixture of composition similar to that produced by the cracking of petroleum hydrocarbons and containing propylene, cooling and separating condensed liquid between the compression stages and combining the liquid thus separated on interstage cooling with the eflluent from the next higher compression stage, cooling the mixed liquid and efliuent from the last compression stage to a temperature sufficient to condense an appreciable quantity of the three carbon atom hydrocarbon, separating the condensed hydrocarbons from the gaseous hydrocarbons and fractionating said condensed hydrocarbons out of contact with the previously separated gaseous hydrocarbons under conditions which will eliminate the said previously separated gaseous hydrocarbons dissolved therein, then separating propylene from the final liquid fraction and recycling same to the fractionating system.

4. The process in accordance with claim 3 characterized in that the gaseous fraction obtained by the rectifying step is combined with the gaseous fraction from the last gas and liquid separation step.

5. The process which comprises compressing in at least three stages a gaseous hydrocarbon mixture containing propylene, lower boiling gaseous components, and polymerizable hydrocarbons, cooling the compressed gases and separating 5 any condensed liquid therefrom between each of the compression stages, combining the liquid thus separated on interstage cooling with the eflluent from the next higher compressionstage, cooling the combined eiliuent and liquid from the lastln compression stage to a temperature sufllcient to condense an appreciable quantity of propylene and separating the resulting liquid from said mixture, fractionating the liquid fraction out of contact with the previously separated gas mixture 18 under conditions that will eliminate any of the gas fraction dissolved therein and retain in the liquid fraction propylene, separating the propylene from this final liquid fraction, and recycling same to the fractionating system.

' 6. The process in accordance with claim 5 characterized in that the gaseous traction obtained by the rectifying step is combined with the gaseous fraction from the last gas and liquid separation step.

DALE F. BABCOCK.

Patent No. 2,222,275.

CERTIFICATE OF CORRECTION.

' November 19, 19119.

DALE F. BABCOCK.

It is hereby certified that error appears in printed specification of the above numbered patent requiring correction as follows: Page 5, first column, line 6, for "35 C; The" read --55 C. the--; and second column,

line 8, for "proylene" read '---propylene--; and that the said Letters Patent should-be read with this correction therein that the same may conform to the record of the case in the Patent Office. Signed and sealed this 23th do? of January, 4. D. 19141,

' Henry Van Aradale, (Seal) Acting Commissioner of Patents. 

